Waterproof compound



Yatenteil May 3, 1938 l g UNITE-D STATES-{PATENT oFFici:

WATERPROOF COMPOUND Maurice Henri Belloc, Paris, France, assignor SocIete-Nobel Francoise, Paris, France,-a jointstock company No Drawing. Application March 2. 1936, Serial No. 66,697. In France March I, 1935 '4 Claims. (oi. 134-13) The present invention has for its object the dicated remains within the scope of the invenpreparation of a waterproofcompound consisting tion by whatever process they are prepared. oi polymerized vinyl derivatives having the Such products have the general formula: chemical composition of acetals.

It is well known to'waterproof paper, fabrics, regenerated cellulose and similar products by I means of varied solutions containing in general 0-on=cn waxes or p fl said compounds are consiiin which R is an aliphatic radical which can be tuted generally by nitrocellulose, a wax or parailln H or according t th th product is and a suitable solvent mixture whi h can als prepared by means of formaldehyde or acetalde- 10 contain 'an oil. F'inally. co p y e used hyde; n is the degree of polymerization of the containing acetate or other cellulose esters or de ti d t; it can vary within wide ethers.- limits.

n r y. waterpr ng coatings of this kin A suitable coating for the purpose proposed 5 contain a cellulose ester or ether associated with in th ef comprise} a wax, a paraflin or an oil. Said coatings have l. One or a plurality of condensation products. a number of drawbacks. of polyvinyl alcohol with formaldehyde, .acetaldey ar n t v ry adh r t. p t y to hyde or a mixture of the two. Said products highly polished'supports such as regenerated celserve as upport 1111056; n Particular y are easily unfitilck by 2. One or a plurality of known waterproofing immersion in water. products such as paramns, natural or synthetic 2- y a e s fli n y flex thisdrewwaxes, chlorinated naphthalenes and the like.

back being pa i u a y p rtant f r wa 3. One or a plurality of plasti'fiers for the proofing fabrics. condensation product; preferably insoluble in 3. The coatings which contain nitrocellulose waten Compounds which are it f th e v yi flfl and, Owing to this fact, intended object are: alkyltoluolsulfonamides, their appli is rather delicatetriphenylphosphate, butyl and cyclohexyl stear- 4. It is rather dimcul p rtic nitroates, and the like. This list is in no way limitace u se cellulose acetate 15 used as a suppm't tive, its object is merely to indicate nominally for the' waterproofing bodies, to find-a compound some of the products which can be used 30 of solvents which dissolve suillciently well, on the 4. A Suitable solvent mixture which comprises. one hand cellulose ester, on the other hand paraiin principle one or a plurality solvents of the is ggiz fi 'g s g gz fg f gg vinyl condensation product, one or a plurality e 0 i 1 eat i the waterrooi'i roduct and of in the preparation of compounds for water of so v o p a p 3,,

proofing papers fabrics, regenerated cellulose the plastiiying product. Amonst the solvents and the like, avoiding to a great extent these 22222 z gfig fi gx g glm ggl drawbacks by using as a support, instead of a th I be m ene e y and meth cellulose ester or ether, a synthetic product hav- 8 i n u t m to 4 ing the chemical composition of a polymerized acetates and the like- It 110 D085! 8 e i 40 vinyl ta], The products g merate all the well lrnown solvents which can Polyvinyl iormals or acetals such as those being (very Varied w ng to the .obtained by reacting aldehydes with more or less fact in parti r that the condensation P dsaponified 'vinyi esters. n ts of polyvinyl alcohol and of aldehyde allow Mixed products such as those obtained by coni of viiry varied solvents acco rding to their con- 45 densing polymerized vinyl esters with two alde- .stitu on. a v hyde's; particularly formaldehyde and acetic If necessary, the compound can also contain paraldehyde. natural or artificial oils or resins, adapted to give It is, of course, understood that the use of it particular properties.

. products having the chemical constitution ln- 1 T e fol ow ne a p ii: e o tions of lo Ethyl ace t desired to water. Y

It is advantageous to heat said compound before use to a suitable temperature so that it's-hall condensation product 600 parts by weight.

Triphenylphosphate- 100 Ethylparatoluenesulfamide 100 Hard paraflln 30 Methanol 600 Benzine 2160 Example 1.As a starting material, the condensation product of vinyl acetate and acetic;- paraldehyde, obtained by adding to 5 kilos, of

polyvinylabetate, 2 litres of water, 1 litre of alcohol and 5 litres of strong hydrochloric acid,

stirring and cooling'and, after a few minutes,- 3 adding 5 kgs. of acetic paraldehyde, then standing 10 hours. at'room temperature.

The following mixture is prepared? 1 Above described condensation product 800 parts by weight.

Hard paraflln v Solvent 8000 Ethylparatoluenesulfamide 150 The solvent will be constituted in this case as follows:

' 5 Volumes 'Toluene 8 This compound can be applied by any means to' paper, regenerated cellulose, fabrics, which it is be completely homogeneous. P

Example 2.As a starting material, a condensation product prepared from a polymerized polyvinylic-acetate such that at 20, a 10% solution of this' compound in ethyl acetate flows in 300 seconds through a hole, through which the same volume of water at the same temperature flows in 15 seconds, by adding to 20 kilos. of this polyvlnylicacetate, 9.6 kilos. of formaldehyde at 40% by volume, 2:55 kgs. of acetic paraldehyde, 4

kgs. of. denatured alcohol and 40 kilos. of hydo chloric acid at-22 Baum, stirring until solution is completed, allowing to remain in contact for 20 The following mixture is prepared: Above described This compound is particularly applicable to the treatment of fabri'cs.- For this use and according to the waterproofing desired, it can, of course, be diluted with .the of methanol and of benzine in the proportions indicated. The appli cation of the solution, preferably hot, will be agreeable aspect.

effected by means of a padding machine. After drying, it is often advantageous to calender in order to givethe waterproofe'd fabric amore Emmple' 3.'As astarting material render substantially impervious to a 1 part waterproofing agent to 16 to'20 parts of said resin, said amount being sufiicient to increase the water resistance of the coating; and a I volatile organic solvent for both the said wateramount hours at room temperature preferably by stirring.

a condensation'product prepared as "in Example 1, by-

benaine, and

substituting 3 kilos. of trioxymethylene for the kgs. of acetic paraldehyde.

The following mixture is prepared: I Above described condensation product 100 1. A resinous liquid coating composition for waterproofing paper, fabrics and regenerated cellulose comprising a resin selected from the group consisting of water insoluble condensation products of'polyvinyl alcohol and acetic paraldehyde, polyvinyl alcohol and a mixture of form-' aldehyde and acetic pal-aldehyde, and polyvinyl alcohol and trioxymethylene; a minor prono 't vn of a waterprooflng'agent selected from the group consisting of paraflin, natural waxes, synthetic waxes, and chlorinated na'phthalenes, said waterproofing agent being present in the proportion of proofing agent and the said resin in suflicient to dissolve the same. v

- 2. A resinous liquid coating composition for waterproofing paper, fabrics and reg'eneratedcellulose'comprising paraflin50 parts by weight, 800 parts by weight 91' the water-insoluble product made by hydrolysis of 5 kilos, of polyvinyl acetate and subsequent condensation with 5 kilos. of

acetic paraldehyde, parts by weight of 'ethy'lparatoluenesulfamide, and 8000 parts by weight of amixture of toluene and ethyl acetate.

3. A resinous liquid coating composition for.

waterproofing paper,- fabrics and regenerated cellulose comprising parailin 30- parts by'weight,

600 parts by weight of the water-insoluble product of simultaneous hydrolysis and condensation of 20 kilos. of polyvinyl acetate with 9.6 kilos. of 40% formaldehyde and 2.55 kilos. of acetic paral dehyde, 100 parts by weight of triphenylphosphate, 100 partsby weight of ethylparatoluenesulfamide, 600 parts by weight of metha-,

no], and 2160 parts by w'eight'of benzine.

4. A resinous liquid coatingco'mposition for waterproofing paper, fabrics and cellulose comprising 9 parts by weight of butyl stearate, 5 parts by weight of polychlotnaphthr lene wax, 100 partsEby weight of the waterinsoluble product of hydrolysis of' 5 kilos. of polyvinyl acetate and subsequent condensation with 3 kilos. of trioxymethylene, -700 parts by weight of methylenechloride, 200 parts by weightof parts .by eight of methanol.

MAURI HENRI BEILOC. 

